SU1516014A3 - Composition for producing dyed articles - Google Patents

Abstract

THE INVENTION RELATES TO THE ANILY-PAINT INDUSTRY. THE INVENTION ALLOWS TO INCREASE COLOR SATURATION 3-6 TIMES WHEN PRESERVING ITS POWERFUL PROPERTIES FOR THE PURPOSE OF RESEARCHES CIRCULATORS AGRICULTURAL 14,4-DIKETOPIRRO (3,4C) PIRDRY CURRENT CURRENT CENTER (3,4С) PIR CIRROSPROD CIRCLE CURRENT .% AND HIGH MOLECULAR ORGANIC MATERIAL REST. 6 TABLE.

Description

or

C1, HQ-s-QbocH3,

SP

is smiling

in the amount of 0.05-10 wt.% and high molecular weight organic material

The invention relates to the paint industry, in particular, to the composition dp for producing colored products.

The purpose of the invention is to increase the saturation of color with preservation of its postochnost properties.

rest. 6 tab.

The composition of dp for obtaining by the production of products contains ivy pigment-1,4-diketopyro (3.4 s) pyrrole of the general formula T

C / 4

where R, and R7 -,

, CNS SGS CN

 13fM

-O-C (CHi, .HQ, 4Q HQN-nQ

About R

OO -Os-Oct,

in the amount of 0.05-10 weight,%.

Compounds of formula T are prepared by heating a nitrile of the formula with a nitrile of the formula RjCN, bromo acetic ester and zinc in an inert organic solvent, preferably in an aromatic hydrocarbon, for example benzene, toluene, xylene.

Preferably, the reaction is carried out in two stages. In the first stage, to a suspension of zinc dust in an organic solvent activated by copper, a mixture of bromoacetic ester, nitramyl and zinc dust is added without air access. Then, heating i for a short time and then, as appropriate, by heating the air for a longer time. The compound of formula 1 can be isolated by filtration.

Depending on the type of substituents and polymers to be colored, the compounds of formula I can be used as soluble in. polymer dyes and, preferably, as pigments. In the latter case, it is advisable to convert the products obtained during the synthesis into a finely dispersed form. It is possible to do this in various known ways.

It is advisable to further treat the pigments with an organic solvent, preferably one that boils above 100 ° C.

Pigments have a BET 5-150 specific surface area.

Example. 1 h. Cu (OOCCHj) tHiO in an Erlenmeyer flask is dissolved in 25 parts by volume. of ethyl acetate at 90 ° C and immediately thereafter mixed with 17.9V h, zinc dust (0.274 mol). The whole mixture is well stirred for 1 min and directly CN

 13fM

-O-C (CHi, .HQ, 4Q HQN-nQ

five

0

50

d -

Afterwards, it is filtered off, washed with a small amount of ethyl acetate and 75 vol. xylene x. Zinc activated in this way is immediately placed in a sulphurization flask with a volume xylene. B dropping an argon current of 15-20 ob.h. mixture consisting of 60 ob.h. xylene, 28 ob.h. benzonitrile (0.27 mol) and 30.4 ob.h. ethyl bromoacetate to 27 mol). The mixture is slowly heated to 60 ° C. The reaction goes exothermically, and the temperature of the contents of the flask quickly rises to approximately 90 ° C. From now on, the temperature is maintained at about 90 ° C, adjusting the rate of addition of the remaining solution of benzoitrile-ethyl ester to bromine and hydrochloric acid. -95 C. Immediately after that, argon is removed and air is passed into the mixture, which is heated to reflux temperature, and stirred for 10 hours at this temperature. Then the mixture is cooled for approximately about 70 ° C and add about 100 vol, h. acetone. The precipitated product is filtered at room temperature, washed with methanol and dried under vacuum overnight at. This gives 10.16 parts of crude product. 3 parts of this product are stirred at room temperature with 100 mp of dimethylformamide containing about 1.8 vol. 30% sodium methylate solution, for 2 h. After crystallization, the filtrate is mixed with H ob.h. ethyl acetate and immediately thereafter with 13 rpm, water and stirred overnight at room temperature. The next morning, the precipitate is filtered off.

it is ethanol, water and ethanol and dried overnight at 80 ° C under vacuum. Compounds of formula 1 (R and R, phenyl) are obtained in a 1.5 hour form of a red powder with a coating surface of 12.

Elementary analysis

Calculated,%: C, 74.99.j, 1 4.22 N, 9.72.

; Cj, H, iNt02, mol. 288.3. Found,%: C 75.0; H 4.4v N 9.8.

UV-spectroscopic analysis (solvent: N-methylpyrrolidone) s .x 504 mm, mWcS3000.

The resulting pigment dyes artificial substances and varnishes in clean cochineal-red tones, which are light resistant, heat resistant and durable when exposed to HIGHLIGHTS.

EXAMPLE 2. 8.8 parts (0.185 mol) of zinc dust are added to a well-stirred hot solution (90-) 0.7 parts of copper acetate - in

The resulting compound paints artificial materials and varnishes in very clean. High intensity bluish-red tones, characterized by light resistance, heat resistance and with high strength to the action of weather conditions.

Example 3. If instead of the example 2 used in b, p-chlorobenzonitri35

12.5 pcs. ethyl acetate. After 1 min, precipitated slurry is precipitated and ethyl acetate is decanted. The residue is washed once with 12.5 ob.h. ethyl acetate and non-benzene are used w-chlorobenzonitrile, then immediately after this three times pores are obtained under the same conditions with wires of 25 vol.h. xylene. The remaining 4 g of the raw pigment, with a gray precipitate together with 65 ml of xy-which is treated as indicated with lola and 18.6 parts (0.135 mol) of p-chlorobenzoitrile are transferred to a sulfonation flask. The mixture is heated approximately until immediately after which 15 vol. Parts is added dropwise. ethyl bromoacetic acid for about 30 minutes so that the temperature in the flask does not exceed 80-85 ° C. At the end of the dropping, the mixture is heated to reflux temperature and the air mixture is passed through the reaction mixture of d5 acid. 18 parts of water are added and the resulting suspension is semi-stirred at this overnight. The next morning at room temperature the mixture is stirred and the mixture is cooled to room temperature overnight. The pigment deposited from the specimen and added to it with stirring is filtered, first washed with 50 parts by volume. Acetoxylene hydroxide with a large amount of dimethylforma- c i immediately after this 40

below.

Example 4. Alkaline reprecipitation.

4h the crude pigment according to example 3 is suspended at 135 rpm, dimethylformamide, mixed with 2.5 rpm. 30% sodium methoxide solution and stirred for 2 hours at room temperature. Immediately thereafter, the solution is clarified through a high flow and the filtrate is neutralized with 4 parts by volume. ice acetic after 15 min from () 1ltrovy and washed on the filter with acetone. The crude product thus obtained is transferred into 250 parts by volume of dimethylformamide and mixed with 5 parts by volume of a 30% sodium methoxide solution and The whole mixture is stirred for 5 minutes. After clarifying filtration, the alkaline clear solution of dimethylformamide is poddoy and ethanol and dried overnight - under a vacuum at 80 ° C. 2.4 hours of an orange-red powder 55 of formula 1 are obtained (R and RI-ha-chlorophenyl ). Elementary analysis.

Calculated: Z: C 60.53 H 2.82i Cl 19.85} N 7.84.

ni, H, eCU NaOi, mol. weight. 357.2,

0

five

five

0

sour 8 vol. glacial acetic acid, diluted with 30 parts by volume water and stirred overnight at room temperature. The red precipitate is filtered off, washed with methanol and dried overnight under vacuum at. Get 3.6 about.h. (15% of theory) of a compound of formula I (R and R 2 is p-chlorophenyl) in the form of a red powder.

Elementary analysis.

Calculated: C 60.53-, H 2.82, N 7.84 j O 8.96i Cl 19.85.

C ,, H, CliNaO ,, mol. 375.21.

Found: C 60.0} H 2.8j N 7.7 O 9.6i C1 19.6.

UV-spectroscopic analysis: (solvent X-methylpyrrolidone): "s, x514 nm," "" "33,000.

The resulting compound paints artificial materials and varnishes in very clean. High intensity bluish-red tones, characterized by light resistance, heat resistance and with high strength to the action of weather conditions.

Example 3. If w-chlorobenzonitrile is used instead of p-chlorobenzonitrior used in Example 2, then 4 g of crude pigment is obtained under the same process conditions, which is treated as indicated with 5% acid. 18 parts of water are added and the resulting suspension is stirred overnight at room temperature. The precipitated pigment is filtered off, washed first with a small amount of dimethyl forma- immediately after this in

w-chlorobenzonitrile is used, then 4 g of crude pigment is obtained under the same process conditions, which is treated as indicated by the acid. 18 parts of water are added and the resulting suspension is stirred overnight at room temperature. The precipitated pigment is filtered off, washed first with a small amount of dimethyl forma- immediately after this in

below.

Example 4. Alkaline reprecipitation.

4h the crude pigment according to Example 3 is suspended at 135 rpm, dimethylformamide, mixed with 2.5 rpm. 30% sodium methoxide solution and stirred for 2 hours at room temperature. Immediately thereafter, the solution is clarified through a high flow and the filtrate is neutralized with 4 parts by volume. glacial acetic acid and ethanol and dried overnight under a vacuum at 80 ° C. Obtain 2.4 hours orange-red powder of formula 1 (R and RI - ha-chlorophenyl). Elementary analysis.

Calculated: Z: C 60.53 H 2.82i Cl 19.85} N 7.84.

ni, H, eCU NaOi, mol. weight. 357.2,

515

Found,%: C 60.0 H.80; C1 19.90; N 7.80.

UV spectroscopic analysis: (solvent N-methylpyrrolidone): "ns512 nm, ,, 27,000.

The obtained pigment from alkaline reprecipitation paints artificial materials and varnishes in red-orange tones with high migration light and heat resistance.

Example 5. Sour reprecipitation.

1.4 parts of the product prepared according to Example 4 are alkaline by reprecipitation of the product suspended in 70 parts by volume. concentrated sulfuric acid and the resulting mixture is stirred for approximately 45 minutes at room temperature. At the end of the clarifying filtration over High flovr (glass filter), the filtrate is poured into approximately 300 parts of ice and stirred for 15 minutes at room temperature. The precipitated pigment is filtered off, washed with water and ethanol and dried overnight in a vacuum at. 1.2 h of red powder is obtained, which has the same elementary analysis data, mass and UV spectrometry and the same chemical structure as the product obtained by alkaline reprecipitation in accordance with Example 4. When carrying out the present acidic reprecipitation, the product is obtained which, in the case of artificial materials and varnishes, gives only pure cochineal-red coloring (instead of orange), as well as resistance to coloring.

The X-ray diffraction pattern of the pigment obtained according to Example 5 shows, at an interplanar distance of 3.22 A, a line of very strong intensity, at 14.3, 6.7 and 3.45 A lines of strong intensity, at 4.72, 4.20, 3.51 and 3.35 X lines of medium intensity, at 5.3 and 2.98 A. lines of weak intensity and at 3.15 A lines of very weak intensity.

X-ray diffraction pattern obtained according to example 4 pigmenta.ta shows at 14.2 and 3.7 A lines of very strong intensity, with 4.72 And the line of strong intensity, with 3.52 And the line of average intensity and at 6.9 And the line of weak intensity.

5 0 5 О д

5 jg

.

five

46

PRI me R 6. Carrying out the method, by analogy with example 5, with the product obtained by alkaline redeposition, according to example 1, a red pigment with a very high staining intensity, transparent, with a specific surface according to CAT 1 is obtained. ten .

Example 7. The applied amount of p-chlorobenzonitrile in example 2 is replaced with an equimolar mixture of p-chlorobenzonitrile and p-methylbenzonitrile under the same process conditions and with the same treatment the red pigment mixture, which according to elemental analysis and mass spectroscopy contains, along with the pigment of formula I (R, and R, is p-chlorophenyl, and R and RI is p-methylphenyl compound of formula G (R, is p-chlorophenyl, RI is P-. toluene).

Mass Spectroscopy: MS; M: 336,

The resulting pigment mixture colors artificial materials and varnishes in red tones of high intensity (saturation) and is distinguished by its color fastness.

PRI me R s 8-37. Analogously to Example 1, other examples of Formula I are obtained by subjecting the nitrile of Formula R-CN to reacting with ethyl bromo-acetic acid in the presence of Zn-Cu, and R has the values listed in Table 1.

PRI me R 38. (Mild polyvinyl chloride). 0.6 g (0.575 wt.%) Of a pigment of the formula I (R, and RJ is phenyl) is mixed with 67 g (64.125 wt.%) Of polyvinyl chloride, 33 g (31.5%) of dioctyl phthalate, 2 g (1, 9%) of dibutyl tin dilaurate and 2 g (1.9%) of titanium dioxide and on a rolling machine for 15 minutes at 160 ° C are processed into a thin film. Get intense red staining, the strength to migrate 5 points. and to the action of light 8 points.

Example 39. (Polyethylene). 0.2 h (0.2%) of pigment of the formula I (R, and phenyl), 1 h. (1.0%) of titanium dioxide rTil and 100 parts (98.8%)

The LD-polyethylene granulate is mixed with U1 in a drum and the mixture is then immediately processed on a mixing roll at 130 ° C. The mass is pressed in hot form to the plates or molded in an extruder. Get a Plas

tiny with a red color, resistant to the action of light.

PRI me R 40. (Polystyrene). 0.05 h, (0.05%) pigment of the formula I (R, and R-Lenyl) are mixed in dry form with 100 parts (99.95%) of polystyrene. The mixture is stirred at 200 - until a homogeneous coloring is obtained. The colored mass is cooled and ground in a mill to a particle size of 2-4 mm. The granulates thus obtained are processed in an injection molding machine at 220-300 ° C to obtain molded products. A red colored mass is obtained. The color possesses good durability to the action of light and thermal stability.

PRI me R 41. (Polyamide) .99,5 h

(99.5%) of polyamide from -caprolactam in the form of pieces is covered with 0.5 part (0.5%) of finely divided pigment of the formula I (R, V, RI is phenyl) in dry form. The thus polished pieces are formed as usual, for example, wet strand at 280-285 ° C. The fiber thus obtained is colored yellow. Coloring fluoresces and has good resistance to the action of light and resistance to wet treatments,

PRI me R 42, (Polycarbonate). 0.05 h, (0.05%) pigment of the formula (R and R, -phenyl) is mixed in dry form with 100 parts (99.95%) of polycarbonate from 2.2 (4,4-dioxydiphenyl propane with a K value about 50 and homogenized in a twin-screw extruder at 280 s, a transparent yellow color is obtained with good durability to the action of light.The granulated product can be processed in the usual way by thermoplastic molding, for example by the method of injection molding to obtain molded products.

EXAMPLE 43, (Alkyd-melamine varnish, hot drying). Mix 60 h, 60% aqueous solution of undried alkyd resin in xylene (Bekozol 27-320 from Reichhold-Albert Chemifc for 36 h, 50% aqueous solution of melamine-form maldehyde resin in a mixture of butenol - xylene (super Bekamin 13-501 from Reichhold -Albert Chemic), 2 parts of xylene and 2 hours, methyl cellosolve, 100 hours

O

five

five

0

the resulting mixture is stirred with a stirrer until a homogeneous varnish solution is obtained.

95 h, (95%) of the clear varnish thus obtained and 5 parts (5%) of the pigment of the formula f (R, and Rj are phenyl) are ground in a ball mill for 72 hours. The painted lacquer is applied by spraying onto the tin and burning 30 min at 120 C. A lacquer coating with good light resistance is obtained.

Example 44, Example 43 is repeated, taking 90 hours, clear varnish and 10 parts of pigment. A lacquer coating with good light fastness and high purity is obtained with a degree of saturation of 566. For comparison, a sample is taken, painted using 90 hours, as described in Example 43 of transparent varnish and 10 hours. red pigment CI 88; The sample indicates the degree of saturation 122.

For dyeing pigments: known formulas

thirty

five

0

five

0

C1

pigment 88)

and

(CI color index

Formula I

where R, H Rj - Rh or

/

-C1R, H Rj used:

a) polystyrene (0.05% pigment) in example 40;

b) polyamide (0.5% pigment) in example 41;

C) polycarbonate (0.05% pigment) in example 42.

No targeted additives were added to the composition.

Table 2 presents the saturation values of the obtained colorings for the degree of purity of the coloring current; the higher the degree of saturation, the cleaner the pigment.

As can be seen from the data in the table, the 2 colors obtained with the proposed compounds — 1,4-dikeopyrrolo (3.4 s) pyrroles, compared to the colors obtained, the sexes with the known pigment — CI pigment-88 — differ from each other. purity (increased degree of saturation).

Table 3 shows the data on the saturation of the color tone during dyeing, polyethylene and varnish with the proposed pigment and tetrachlorothioindigo

Polyethylene was dyed according to example 39, varnish was dyed according to example A3,

Table 4 shows the color saturation values.

In Example 38, 0.2% soft polyvinyl chloride pulps were made, in Example 43, lacquer strips of alkyl melamine formaldehyde resin,

Table 5 shows the values of the pigments.

in the following ratio, wt.%:

The specified pigment 0.05-10.00

ten

The color data of the pigments according to the invention are presented in table 6.

Claims (1)

Invention Formula A composition for obtaining colored products based on high molecular weight organic material and a pigment of a series of five-membered heterocyclic compounds with diketo groups, characterized in that, in order to increase the degree of color saturation while retaining its strength properties, it contains 1,4-diketopyrrolo as a pigment (3,4 t) pyrrole of general formula SNS CN -Kj / VN. HQN, -O High molecular weight organic material Table 1 Rest 507 472 535 500 554,512 / S-naphthyl 3-Trifluoromethylphenyl 4-fluorophenyl 4-benzoylaminophenyl 4-tert-butyl-phenyl 3,4-Dimesh1phenyl R, is phenyl, R - p-toluyl 4-methylsulfonyl phenyl 3-methoxycarbonylphenyl 4-Methoxycarbo nephenyl 3,4-dimethoxy-phenyl 3,4,5-Trimetoxyphenyl 3-Chloro-4-methylphenyl 4-Methoxyfefcyl 4-Acetoxyphenyl 4-acetylaminophenyl 3-Cyanphenyl p-Methylmercaptophenyl p-phenoxyphenyl - w-phenoxyphenyl p-phenylmercaptothenl 472 525 485 473 492 531 477 512 474 508 494 533 492 582 6 | R 475 512 Have 7 / Red , And note; All measurements were made in N-methylpyrrolidone, except for Example 10 (in dimethylformamide), Table 2 Pigment saturation polysp-j-polycarbonol debonate (0.05%) (0.5%) (0.05%) Known 517 39 623 Predpagaye -ch9 504 909 (K, and Rj-Ph; The same 550 560 781 (R ciTable3 Saturation pigment polyethylene varnish Tetrachlorortioindigo312151 Offered where R and R 508598 phenyl СНз-О, С1- / Л | R 475 512 509 501 644 562 151601416 TableA . Saturation Saturation at “0.02% at 20% in PVC in 20 / 5th printing ink oindi- 221 461 417 76A 36733 345726 Table5 Saturation and R.J in lacquer in the polyis of alkylmethyl-hporid-J amino formaldehyde film Oj2% resin 0.2% 45 46 771 398 407 658 723 639 51 52 53 54 55 56 p-Bromophenyl 54158 3-Trifluoromethylphenyl 73158 p-Methoxyphenyl 65858 t-cyanphenyl 70658 T a b l and c a 6 S 9 37 lg 471 a.8 8